1,3,4,-thiadiazolylazo dyes and ink compositions containing the same

ABSTRACT

A dye of Formula (1):                    
     R 1  and D are each independently H or a substituent; 
     R 2  and R 3  are each independently optionally substituted alkyl, aryl or aralkyl, or R 2  and R 3  together with the carbon atom to which they are attached form an optionally substituted ring; 
     R 4  is H or optionally substituted alkyl, aryl or aralkyl; and 
     R 5  and R 6  are each independently optionally substituted alkyl, aryl or aralkyl. 
     Also claimed are compositions containing the dye, water and a water-dissipatable polymer.

This application is the national phase of international applicationPCT/GB99/00772 filed Mar. 15, 1999 which designated the U.S.

This invention relates to compositions, dyes, cartridges, ink jetprinters and to their use in ink jet printing.

Ink jet printing methods involve a non-impact printing technique forprinting an image onto a substrate using ink droplets ejected through afine nozzle onto a substrate without bringing the nozzle into contactwith the substrate.

There are many demanding performance requirements for dyes and inks usedin ink jet printer. For example they should desirably exhibit some orall of the following properties. They should provide sharp,non-feathered images having good water-fastness, light fastness and/oroptical density. The inks are often required to dry quickly when appliedto a substrate to prevent smudging, but they should not form a crustover the tip of an ink jet nozzle because this will stop the printerfrom working. The inks should also be stable to storage over timewithout decomposing or forming a precipitate which could block the finenozzle. The most popular ink jet printers are the thermal andpiezoelectric ink jet printers.

We have now found that very good ink jet printing inks may be preparedhaving the compositions defined below using a specific class of dyesthat give stable dye resin inks with some or all of these advantageousproperties.

According to the present invention there is provided a compositioncomprising water, a water-dissipatable polymer and one or more dyes ofFormula (1):

wherein:

R¹ and D are each independently H or a substituent;

R² and R³ are each independently optionally substituted alkyl, aryl oraralkyl, or R² and R³ together with the carbon atom to which they areattached form an optionally substituted ring;

R⁴ and R⁵ are each independently H or optionally substituted alkyl, arylor aralkyl; and

R⁶ is optionally substituted alkyl, aryl or aralkyl.

When R¹ or D is a substituent it is preferably halo; optionallysubstituted alkyl, aryl or aralkyl; or a group of formula —X—R⁷ whereinX is O, S, SO, SO₂ or NR⁸ wherein R⁷ and R⁸ are each independently H oroptionally substituted alkyl, aryl or aralkyl.

When R¹, R², R³, R⁴, R⁵, R⁶, R⁷ or R⁸ is optionally substituted alkyl itis preferably optionally substituted C₁₋₆-alkyl.

When R¹, R², R³, R⁴, R⁵, R⁶, R⁷ or R⁸ is optionally substituted aryl itis preferably optionally substituted C₆₋₁₂-aryl, more preferablyoptionally substituted phenyl or naphthyl.

When R¹, R², R³, R⁴, R⁵, R⁶, R⁷ or R⁸ is optionally substituted aralkylit is preferably optionally substituted benzyl or xylyl.

R¹ and D are preferably each independently H, optionally substitutedC₁₋₆-alkyl, or a group of formula —X—R⁷ wherein X is O, S, SO, SO₂ orNR⁸ wherein R⁷ and R⁸ are each independently H or optionally substitutedC₁₋₆-alkyl.

X is preferably O, S or NR⁸ wherein R⁸ is H or C₁₋₆-alkyl.

R² and R³ are preferably each independently optionally substitutedC₁₋₆-alkyl, or R² and R³ together with the carbon atom to which they areattached form an optionally substituted 5- or 6-membered ring,especially an optionally substituted cyclopentane or cyclohexane ring.

R⁴ and R⁵ are preferably each independently H or optionally substitutedC₁₋₆-alkyl, more preferably H or C₁₋₆-alkyl.

R⁶ is preferably optionally substituted C₁₋₆-alkyl, more preferablyC₁₋₆-alkyl.

R⁷ is preferably optionally substituted C₁₋₆-alkyl, more preferablyoptionally substituted C₁₋₄-alkyl.

R⁸ is preferably H or C₁₋₆-alkyl.

The optional substituents which may be present on R¹ to R⁸ or on D arepreferably each independently selected from carboxy, sulpho, nitro, halo(especially bromo, chloro and fluoro), alkyl (especially C₁₋₄-alkyl),alkoxy (especially C₁₋₄-alkoxy), hydroxy, amine (especially —NHR⁹),mercapto, thioalkyl (especially C₁₋₄-thioalkyl), cyano, ester(especially —OCOR⁹ or —COOR⁹) and amide (especially —CONHR⁹), wherein R⁹is H or optionally substituted C₁₋₄-alkyl (preferably H or C₁₋₄-alkyl).

In one embodiment of the present invention R² and R³ are free from thefollowing substituents: —NO₂, —CN, —Cl, —Br, —F, —OH, —OC₁₋₄-alkyl,—CONH(C₁₋₄-alkyl), —CONH₂, —COOC₁₋₄—(CH₂)₁₋₄—CN, —OCO(C₁₋₄-alkyl) and—COO(C₁₋₄-alkyl).

In a second embodiment of the present invention at least one of R² andR³ carries a substituent selected from —NO₂, —CN, —Cl, —Br, —F, —OH,—OC₁₋₄-alkyl, —COOC₁₋₄—(CH₂)₁₋₄—CN, —CONH₂, —CONH(C₁₋₄-alkyl),—OCO(C₁₋₄-alkyl) and —COO(C₁₋₄-alkyl).

The preferred optional substituents for R⁸ are said optionalsubstituents are each independently selected from carboxy, sulpho,nitro, halo, alkyl, alkoxy, hydroxy, amine, mercapto, thioalkyl, cyano,ester and amide, more preferably from —NO₂, —CN, —Cl, —Br, —F, —OH,—OC₁₋₄-alkyl, —OC₁₋₄-alkylene—CN, —CONH₂, —COOC₁₋₄—(CH₂)₁₋₄—CN,—OCO(C₁₋₄-alkyl) and —COO(C₁₋₄-alkyl), especially from —CN and—COO(C₁₋₄-alkyl), especially —CN. Preferably R⁸ carries one or twosubstituents, more preferably one substituent.

Any alkyl groups in dyes of Formula (1) may be branched or straightchain. Preferred branched chain alkyl groups are α-branched alkylgroups.

The dyes may be in any form, for example in the form of a salt. Formula(1) includes all tautomers, stereoisomers, zwitterions, polymorphs, andisotopes of dyes falling within the formula.

Salts of Formula (1) may be formed from one or more organic and/orinorganic bases or acids. Preferred salts of Formula (1) are insolublein water.

The compositions preferably contain from 1 to 10, more preferably from 1to 6, especially from 1 to 3, more especially 1 dye of Formula (1).

The dye of Formula (1) is preferably insoluble in water and soluble inthe water-dissipatable polymer. Therefore the dye is preferably freefrom carboxy and sulpho groups, for example it is preferably a disperseor solvent-soluble dye. Disperse and solvent soluble dyes are distinctfrom pigments in that pigments are insoluble in organic solvents andpolyesters whereas disperse and solvent soluble dyes are soluble inorganic solvents and polymers.

According to a second feature of the present invention there is provideda dye of Formula (1) as hereinbefore defined. The preferences for thedye of Formula (1) are as hereinbefore described in relation to thepreferred dyes used in the inks of the invention.

The dyes of Formula (1) may be prepared by diazotising a suitable amine,using a diazotising agent, preferably below 5° C., and coupling to asuitable coupling component. A preferred diazotising agent is sodiumnitrite. A suitable amine is of Formula (2) and a suitable couplingcomponent is of Formula (3):

wherein R¹, R², R³, R⁴, R⁵, R⁶ and D are as hereinbefore defined.

Generally from 3 to 5 molar equivalents of the amine are used relativeto the amount of the coupling component. If desired the resultant dyemay be further reacted, for example by condensation with an acyl halideor an anhydride to convert some or all of any hydroxy groups to estergroups.

The composition may contain further dyes other than those of Formula(1), although this is not normally necessary.

The water-dissipatable polymer preferably bears ionised carboxy and/orsulphonate groups, especially ionised sulphonate groups, because theseassist water dissipatability of the polymer. Such groups can be chainpendant and/or terminal.

The water-dissipatable polymer is preferably a water-dissipatablepolyester. The water-dissipatable polyester can be prepared usingconventional polymerisation procedures known to be effective forpolyester synthesis. Thus, it is well known that polyesters containcarbonyloxy (i.e. —C(═O)—O—) linking groups and may be prepared by acondensation polymerisation process in which an acid component(including ester-forming derivatives thereof) is reacted with a hydroxylcomponent. The acid component may be selected from one or more polybasiccarboxylic acids, e.g. di- and tri-carboxylic acids or ester-formingderivatives thereof, for example acid halides, anhydrides or esters. Thehydroxyl component may be one or more polyhydric alcohols or phenols(polyols), for example, diols, triols, etc. (It is to be understood,however, that the polyester may contain, if desired, a proportion ofcarbonylamino linking groups —C(═O)—NH— (i.e. amide linking groups) byincluding an appropriate amino functional reactant as part of the“hydroxyl component”; such as amide linkages). The reaction to form apolyester may be conducted in one or more stages. It is also possible tointroduce in-chain unsaturation into the polyester by, for example,employing as part of the acid component an olefinically unsaturateddicarboxylic acid or anhydride.

Polyesters bearing ionised sulphonate groups may be prepared by usingthe method, and using the materials, described in International PatentPublication number WO 98/14525 of Zeneca Limited, page 11, line 15, topage 13, line 7, which is incorporated directly herein by referencethereto.

Polyesters bearing ionised carboxy groups can be prepared by variousmeans, for example by the method, and using the materials, described inInternational Patent Publication number WO 98/14525 of Zeneca Limited,page 13, line 9 to page 13, line 30, which is incorporated directlyherein by reference thereto.

The water-dissipatable polyester may optionally have hydrophilicnon-ionic segments, for example within the polyester backbone (i.e.in-chain incorporation) or as chain-pendant or terminal groups. Suchgroups may act to contribute to the dispersion stability or evenwater-solubility of the polyester. For example, polyethylene oxidechains may be introduced into the polyester during its synthesis byusing as part of the hydroxyl component, ethylene oxide-containing mono,di or higher functional hydroxy compounds, especially polyethleneglycols and alkyl ethers of polyethylene glycols, examples of whichinclude:

wherein R⁸ is C₁₋₂₀-alkyl, preferably C₁₋₄-alkyl, more preferablymethyl; n is 1 to 500; and p is 1 to 100.

A small segment of a polyethylene oxide chain could be replaced by apropylene oxide or butylene oxide chain in such non-ionic groups, butshould still contain ethylene oxide as a major part of the chain.

The amount of ionised sulphonate and/or carboxy groups present in thepolyester should be sufficient to provide or contribute towater-dissipatability of the polyester, although it should not be sohigh as to render the resulting polyester unacceptably water-sensitive.This amount will depend, inter alia, on factors such as thehydrophilicity/hydrophobicity of units provided by other monomers in thepolyester synthesis or any surfactants (if used), and also the relativeproportions of ionised sulphonate/carboxy groups. With regard to thelast mentioned point, ionised sulphonate groups are more effective atproviding or contributing to water-dissipatability than ionised carboxygroups and so can be used at considerably lower levels in comparison toionised carboxy groups.

If the polyester is wholly or predominantly sulphonate stabilised (bywhich is meant the water dissipatability-providing groups are providedwholly or predominately by ionised sulphonate groups). The ionisedsulphonate group content is preferably as described in InternationalPatent Publication number WO 98/14255 of Zeneca Limited, page 14, line31 to page 15, line 3, which is incorporated directly herein byreference thereto.

If the polyester is predominantly stabilised by ionised carboxy groups,the carboxylic acid value AV of the polyester is preferably within therange of from 20 to 140 mgKOH/g (more preferably 30 to 100 mgKOH/g).

Usually, the polyester is either predominantly sulphonate-stabilised orpredominantly carboxylate stabilised (preferably the former).

If the polyester contains polyethylene oxide chains, the polyethyleneoxide chain content should preferably not exceed 25% by weight (and morepreferably should not exceed 15% by weight), based on the total weightof the polyester, in order to avoid unacceptable water-sensitivity.Therefore the amount is preferably 0 to 25% by weight (more preferably 0to 15% by weight) based on the total weight of polyester.

The water-dissipatable polyester preferably has a number averagemolecular weight Mn of up to 30,000. The Mn is preferably in the rangefrom 500 to 30,000, more preferably 1,000 to 25,000. These Mn lead toparticularly good storage stability for the resultant inks. Themeasurement of Mn is well known to those skilled in the art, and may forexample be effected using gel permeation chromatography in conjunctionwith a standard polymer such as polystyrene or polymethylmethacrylate ofknown molecular weight.

The water-dissipatable polyester preferably has a hydroxyl number offrom 0 to 225 mg KOH/g, more preferably 0 to 125 mg KOH/g, especiallyfrom 0 to 50 mgKOH/g.

The ink preferably has a pH of 5 to 9, more preferably 5.5 to 8,especially 6 to 7.5. These preferences are based on increased inkstability.

The Tg of the water-dissipatable polyester (i.e. the temperature atwhich the polymer changes from a glassy, brittle state to a plastic,rubbery state) is preferably in the range −38° C. to 105° C., morepreferably −20 to 70° C., especially −10° C. to 60° C.

The esterification polymerisation processes for making the polyestersfor use in invention composition are known and need not be describedhere in more detail. Suffice to say that they are normally carried outin the melt using catalysts, for example a tin-based catalyst, and withthe provision for removing any water or alcohol formed from thecondensation reaction.

The water-dissipatable polyester may be dissipated in water by addingthe solidified melt directly into water. The solidified melt ispreferably in a form such as flake (which can often be obtained directlyfrom the melt) or comminuted solid (obtained for example by grinding).Alternatively, water can be added directly to the hot polyester meltuntil the desired solids content/viscosity is reached. Still further,the polyester may be dissipated in water by adding an aqueouspre-dissipation (or organic solvent solution) of the polyester to thewater phase.

The water-dissipatable polyesters normally do not need an externalsurfactant when being dissipated into water, although such surfactantsmay be used to assist the dissipation if desired and in some cases canbe useful in this respect because additional surfactants reduce therequired amount of dissipating groups (i.e. sulphonate, and (monoalkoxy)polyalkylene chains if used).

The water-dissipatable polymer may also be formed by the method, andusing the materials, described in International Patent Publicationnumber WO 98/14525 of Zeneca Limited, page 16, line 8 to page 16, line34, which is incorporated directly herein by reference thereto.

The dyed water-dissipatable polymer may be prepared by heating awater-dissipatable polymer and dye(s) at an elevated temperature, forexample at a temperature in the range 35 to 150° C., preferably from 40to 90° C. Simply mixing the dye and polymer in water at room temperatureleads to a slight up-take of colour but heating is usually necessary fora full dyeing.

Preferably compositions according to the invention are prepared bymixing together (i) a solution of a dye(s) in a water-immiscible solventand (ii) a mixture of a water-dissipatable polymer, water-misciblesolvent and optionally water. Equally the compositions may be preparedby mixing together (i) a solution of a dye(s) in a mixture of awater-miscible solvent and a water-immiscible solvent and (ii) awater-dissipatable polymer and optionally water. In either case, ifthere is no water in component (ii) the water may be added to themixture of (i) a (ii) subsequently to give acomposition according to theinvention. However it is preferred for component (ii) to contain water.These processes lead to particularly good up-take of dye(s) by thepolymer to give intensely coloured composition.

The amount of dye and water-dissipatable polymer contained in thecomposition will vary according to the depth of shade required.Typically, however, the composition will comprise

(a) from 0.5 to 15 parts, more preferably 0.8 to 10 parts, especially 1to 5 parts in total of the dye(s);

(b) from 0.2 to 25 parts, more preferably 2 to 15 parts of awater-dissipatable polymer;

(c) from 40 to 90 parts, more preferably from 50 to 80 parts of water;and

(d) from 0 to 60 parts, more preferably 0 to 40 parts of organicsolvent;

wherein all parts are by weight and the total number of parts of(a)+(b)+(c)+(d) add up to 100.

The number of parts of the water-dissipatable polymer is calculated on a100% solids basis. For example 50 g of a 20% solids polymer is taken as10 g of polymer.

The composition may also contain an organic solvent (as mentioned in (d)above) and this may be a mixture of organic solvents. In a preferredembodiment the composition contains an organic solvent comprising awater-miscible organic solvent and a water-immiscible organic solvent.

Suitable water-immiscible organic solvents include aromatichydrocarbons, e.g. toluene, xylene, naphthalene, tetrahydronaphthaleneand methyl naphthalene; chlorinated aromatic hydrocarbons, e.g.chlorobenzene, fluorobenzene, chloronaphthalene and bromonaphthalene;esters, e.g. butyl acetate, ethyl acetate, methyl benzoate, ethylbenzoate, benzyl benzoate, butyl benzoate, phenylethyl acetate, butyllactate, benzyl lactate, diethyleneglycol dipropionate, dimethylphthalate, diethyl phthalate, dibutyl phthalate, di (2-ethylhexyl)phthalate; alcohols having six or more carbon atoms, e.g. hexanol,octanol, benzyl alcohol, phenyl ethanol, phenoxy ethanol, phenoxypropanol and phenoxy butanol; ethers having at least 5 carbon atoms,preferably C₅₋₁₄ ethers, e.g. anisole and phenetole; nitrocellulose,cellulose ether, cellulose acetate; low odour petroleum distillates;turpentine; white spirits; naphtha; isopropylbiphenyl; terpene;vegetable oil; mineral oil; essential oil; and natural oil; and mixturesof any two or more thereof. Benzyl alcohol is especially preferred.

Suitable water-miscible organic solvents include C₁₋₅-alkanols, e.g.methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol,tert-butanol and isobutanol; amides, e.g. dimethylformamide anddimethylacetamide; ketones and ketone alcohols, e.g. acetone anddiacetone alcohol; C₂₋₄-ether, e.g. tetrahydrofuran and dioxane;alkylene glycols or thioglycols containing a C₂-C₆ alkylene group, e.g.ethylene glycol, propylene glycol, butylene glycol, pentylene glycol andhexylene glycol; poly(alkylene-glycol)s and thioglycol)s, e.g.diethylene glycol, thiodiglycol, polyethylene glycol and polypropyleneglycol; polyols, e.g. glycerol and 1,2,6-hexanetriol; and lower alkylglycol and polyglycol ethers, e.g. 2-methoxyethanol,2-(2-methoxyethoxy)ethanol, 2-(2-ethoxyethoxy) ethanol,2-(2-butoxyethoxy)ethanol, 3-butoxypropan-1-ol,2-[2-(2-methoxyethoxy)-ethoxy]ethanol,2-[2-(2-ethoxyethoxy)ethoxy]-ethanol; cyclic esters and cyclic amides,e.g. optionally substituted pyrollidones; sulpholane; and mixturescontaining two or more of the aforementioned water-miscible organicsolvents. Preferred water-miscible organic solvents are C₁₋₆-alkyl monoethers of C₂₋₆-alkylene glycols and C₁₋₆-alkyl mono ethers ofpoly(C₂₋₆-alkylene glycols).

Component (d) of the above mentioned composition preferably comprises;

(i) 5 to 50% of a water-immiscible alcohol having at least six carbonatoms, (especially benzyl alcohol); and

(ii) 50 to 95% of a water-miscible solvent comprising;

(a) a cyclic ester or cyclic amide (especially an optionally substitutedpyrrolidone);

(b) a water-miscible C₁₋₆-alkyl mono ether of a C₂₋₆-alkylene glycol orC₁₋₆-alkyl mono ether of poly(C₂₋₆-alkylene glycol); or

(c) a mixture of (a) and (b).

wherein all % are by weight and add up to 100%.

The water-immiscible solvent preferably has a solubility in water at 20°C. of up to 50 g/l. The water-miscible solvent preferably has asolubility in water at 20° C. of more than 50 g/l.

The preferred optionally substituted pyrrolidones, are 2-pyrrolidone,dimethyl pyrrolidone, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone andN-(2-hydroxyethyl)-2-pyrrolidone and mixtures thereof.

The ratio of water-miscible organic solvent to water-immiscible organicsolvent is preferably 19:1 to 1:1, more preferably 8:1 to 1:1,especially 5:1 to 1:1.

Use of dyes has advantages over the use of pigments in that less dye isusually required than would be the case for a pigment, expensive millingis avoided, the composition are less likely to form a precipitate onstanding, a far greater variety of shades are available and theresultant prints have good transparency. The composition of the presentinvention also benefit from good light- and water-fastness.

A valuable feature of the invention is the low tendency for blocking thenozzles of thermal ink jet printers. Many other water dispersiblepolymer composition work poorly or even not at all in thermal printers.Composition of the invention form discrete droplets on the substratewith little tendency for diffusing. Consequently sharp images can beobtained, resulting in excellent print quality and little if any bleedbetween colours printed side-by side.

Preferably the composition is an ink, more preferably an ink jetprinting ink. When the composition is not an ink it may be used asconcentrated colorant for the preparation of an ink.

Preferably the composition has been filtered through a filter having amean pore size below 10 μm, more preferably below 5 μm especially below2 μm, more especially below 1 μm. In this way reliability of the ink jetprinter is improved by removing particulate matter which could otherwiseblock the fine nozzles of the printer.

A third feature of the invention provides a composition comprising awater dissipatable polymer and a dye as hereinbefore defined, preferablyof Formula (1). In these compositions the preferred water-dissipatablepolymers and dyes are as hereinbefore described. Such compositions maybe dissipated in water and optionally mixed with further ingredients togive an ink, for example with one or more organic solvents.

The composition of the third feature of the present invention preferablycomprises (a) 0.125 to 40 parts of a dye as hereinbefore defined(preferably of Formula (1) or (2)); and (b) 99.875 to 60 parts of awater-dissipatable polymer, wherein the total number of parts of (a) and(b) adds up to 100.

According to a further feature the present invention provides a processfor printing an image on a substrate comprising applying thereto acomposition comprising water, a water-dissipatable polymer and a dye ashereinbefore defined (preferably of Formula (1) or (2)) by means of anink jet printer.

The ink jet printer emits droplets of the composition onto a substratefrom a nozzle without bringing the nozzle into contact with thesubstrate. Preferably the ink jet printer is a thermal or piezoelectricink jet printer.

The substrate is preferably a paper, an overhead projector slide or atextile material. Preferred textile materials are cotton, polyester andblends thereof.

When the substrate is a textile material the process for printing animage thereon according to the invention preferably further comprisesthe step of heating the resultant printed textile, preferably to atemperature of 50° C. to 250° C.

A further feature of the present invention is a cartridge suitable foruse in an ink jet printer containing acomposition according to theinvention. Also there is provided an ink jet printer containingacomposition according to the invention.

The invention is further illustrated by the following examples in whichall parts and percentages are by weight unless specified otherwise.

Water-Dissipatable Polymer (“Resin 1”)

To a glass reactor fitted with distillation column and condenser werecharged ingredients A, B, D, F, G and 50% of C and 50% of H. Thecontents were heated with stirring to a reaction temperature of 210° C.until the mixture was clear and the acid value was <10 mg(KOH)g⁻¹. Atthis point E and the remainder of C and H were charged and thetemperature raised to 230° C. The reaction was continued under reducedpressure until an acid value of 5.3 mg(KOH)g⁻¹ was obtained. The resinwas further characterised by a hydroxyl value=27.6 mg(KOH)g⁻¹, ICI Coneand Plate viscosity @125° C.=80 poises and a Tg (onset)=25.4° C. and anumber average molecular weight by end group analysis of approximately2000. The resin was readily dispersed in warm distilled water to give aclear solution having a solids content of 20% w/w (hereinafter “Resin1”).

Resin 1 Monomer Abbreviation Weight (g) Neopentyl glycol A 206.25Diethylene glycol B 82.5 Isophthalic acid C 300Sodio-5-sulpho-isophthalic acid D 75 Adipic acid E 37.5 Methoxy PEG 750F 75 Sodium acetate G 1.5 Fascat 4101 H 0.75

Water-Dissipatable Polymer (“Resin 2”)

To a glass reactor fitted with distillation column and condenser werecharged ingredients A, B, C, E, G, H and 50% of D and 50% of I. Thecontents were heated with stirring to a reaction temperature of 210° C.until the mixture was clear and the acid value was 1.25 mg(KOH)g⁻¹. Atthis point F and the remainder of D and I were charged and thetemperature raised to 230° C. The reaction was continued under reducedpressure until an acid value of 2.8 mg(KOH)g⁻¹ was obtained. The resinwas further characterised by a hydroxyl value=19.7 mg(KOH)g⁻¹, ICI Coneand Plate viscosity @125° C.=90 poises and a Tg (onset)=4° C. The resinwas readily dispersed in warm distilled water to give a clear solutionhaving a solids content of 20% w/w. (hereinafter “Resin 2”).

Resin 2 Monomer Abbreviation Weight (g) Neopentyl glycol A 653.47Diethylene glycol B 479.21 Hexane-1,6-diol C 396.04 Isophthalic acid D1584.16 Sodio-5-sulpho-isophthalic acid E 396.04 Adipic acid F 198.02Methoxy PEG 750 G 396.04 Sodium acetate H 8 Fascat 4101 I 4

Water-Dissipatable Polymer (“Resin 3”)

To a glass reactor fitted with distillation column and condenser werecharged ingredients A, B, D, E, F, G and 50% of C and 50% of H. Thecontents were heated with stirring to a reaction temperature of 210° C.until the mixture was clear and the acid value was <10 mgKOH/g. At thispoint the remainder of C and H were charged and the temperature raisedto 230° C. The reaction was continued under reduced pressure until anacid value of 9.4 mg(KOH)g⁻¹ was obtained. The resin was furthercharacterised by a hydroxyl value=12.8 mg(KOH)g⁻¹, ICI Cone and PlateViscosity @125° C.=>500 poises and a Tg (onset)=18° C. The numberaverage molecular weight as determined by gel permeation chromatography(PS Equivalents) was 1800. The resin was readily dispersed in warmdistilled water to give a clear solution having a solids content of 20%w/w (hereinafter “Resin 3”).

Resin 3 Monomer Abbreviation Weight (g) Neopentyl glycol A 15 Diethyleneglycol B 10 Isophthalic acid C 45 Sodio-5-sulpho-isophthalic acid D 10Hexane-1,6-diol E 10 Methoxy PEG 750 F 10 Sodium acetate G 0.2 Fascat4101 H 0.1

EXAMPLE 1 Preparation of a Dye of the Following Formula Dye 1

(a) Preparation of 3-(N-n-Butyl-N-sec-butylamino)Acetanilide

(i) 3-(N-sec-Butylamino)acetanilide

3-Aminoacetanilide (186.2 g), 2-bromobutane (198 g), triethylamine (150g) and ethanol (1 liter) were heated under reflux for 64 hours. Aftercooling to room temperature, the reaction mixture was filtered to removetriethylamine hydrochloride and the solvent was evaporated under reducedpressure to leave a dark oil which was purified by chromatography onsilica gel. The product was crystallised by trituration under hexane togive 152 g of product.

(ii) 3-(N-n-Butyl-N-sec-butylamino)Acetanilide

3-(N-sec-butylamino)acetanilide from stage (a) (i) (20.6 g),1-bromobutane (63.7 g) and anhydrous potassium carbonate (13.8 g) werestirred and heated under reflux for 36 hours. The cooled reactionmixture was diluted with methanol (50 ml) and filtered to remove theinorganic salts. Evaporation of the excess bromobutane and methanolunder reduced pressure gave a viscous oil which was purified bychromatography on silica gel to give 18.3 g of product.

(b) Preparation of Title Dye

Acetic acid (100 ml), propionic acid (16.0 ml) and nitrosyl sulphuricacid (22.9 ml) were stirred together whilst lowering the temperature to0-5° C. Amine of formula

(11.1 g available commercially from Maybridge Chemical Company, usedwithout further purification) was added portionwise to the mixture, withthe temperature kept at 0-5° C. Once addition was completed the reactionmixture was stirred at 0-5° C. for 2 hours and the excess nitrous aciddestroyed with sulphamic acid. The resulting diazonium salt solution wasslowly added to a solution of 3-(N-n-butyl-N-sec-butylamino)acetanilide(13.1 g from stage (a)(ii) above) in methanol (400 ml) at 0-5° C. Whenaddition was complete the pH was raised to 4.5 by the addition of sodiumacetate and the reaction mixture was stirred for 2 hours at 0-5° C. Thereaction was diluted with water (500 ml) and stirred for one hour. Thecrude product was isolated by extracting into dichloromethane andpurified by column chromatography on silica gel (2% methanol indichloromethane was used as the eluent) to give the title dye (3.5 g) asan oil having a λmax at 528 nm.

EXAMPLE 2 Preparation of a Dye of the Following Formula Dye 2

(a) Preparation of 2-Amino-5-cyanomethylthio-1,3,4-thiadiazole

Chloroacetonitrile (45.8 g) was added dropwise to a solution of5-amino-1,3,4-thiadiazole-2hiol (67.9 g) in ethanol (500 ml) at refluxtemperature. The reaction mixture was heated under reflux for 6 hoursand then approximately 400 ml of distillate was removed using aDean-Stark trap. The reaction mixture was allowed to cool, water (150ml) was added and the pH was adjusted to 7.0 with sodium carbonate. Theresultant precipitate was collected by filtration, washed with water anddried to give 45.7 g of product which was used directly in the nextstep.

(b) Preparation of Title Dye

The title dye was prepared analogously to the method described inExample 1, stage (b) above, using 12.9 g of2-amino-5-cyanomethylthio-1,3,4-thiadiazole (from Example 2, stage (a)above) and 16.4 g of 3-(N-n-butyl-N-sec-butylamino)acetanilide [fromExample 1, stage 1 (a) above] to give, as a green solid, 6.1 g of thetitle dye having a λmax at 532 nm.

EXAMPLE 3 Dye 3

Dye 3 was prepared using the method described in Example 1 except thatin stage a there was used isopropylbromide and allyl bromide in theplace of 2-bromobutane and 1-bromobutane respectively. The title dye hada λmax at 524 nm.

EXAMPLE 4 Dye 4

Dye 4 was prepared using the method described in Example 2 except thatin the place of 1-bromobutane there was used 2-bromobutane. Theresultant dye had a λmax at 532 nm.

EXAMPLE 5 Dye 5

Dye 5 was prepared using the method described in Example 2 except that3-(N-n-butyl-N-sec-butylamino) acetanilide was hydrolysed in thepresence of base and then reacted with ethyl chloroformate. Theresultant dye had a λ at 531 nm.

EXAMPLE Dye 6

Dye 6 was prepared using the method described in Example 1 except thatin stage a there was used isopropylbromide and alkyl bromide in theplace of 2-bromobutane and 1-bromobutane respectively, and that2-amino-5-ethylthio-1,3,4-thiadiazole was used in place of the amineused in stage (b). The resultant dye had a λmax at 522 nm.

EXAMPLE 7 Dye 7

Dye 7 was prepared using the method described in Example 2 except thatin stage (a) sodium chloroacetate was used in place ofchloroacetonitrile. The resultant dye had a λmax at 501 nm.

EXAMPLE 8 Dye 8

Dye 8 was prepared using the method described in Example 2 except thatin stage (a) methoxyethoxyethoxyl ethyl chloride was used in place ofchloroacetonitrile. The resultant dye had a λmax at 527 nm.

EXAMPLE 9 Preparation of Inks

The following abbreviations are used:

XA is Xerox 4024 paper from Rank Xerox;

GB is Gilbert Bond paper from the Mead Corporation;

WC is Wiggins Conqueror High White Wove 100 gm⁻² paper from Arjo WigginsLtd; and

“-” means not measured;

OD means optical density;

LF means light fastness;

ΔE is the time in hours over which the LF is measured; and

WF: Wet fastness.

Each dye or dye mixture was dissolved in benzyl alcohol and2-pyrrolidone. The water-dissipatable polyester was dissipated in waterand then mixed with the dye solution and shaken to give the homogeneousink.

Table 1 below shows the final formulation of an ink (ink 1) prepared asabove. The first column identifies the component and the subsequentcolumns show the amount in parts by weight of each component in theresultant ink.

TABLE 1 Component Ink 1 Ink 2 Ink 3 Ink 4 Ink 5 Ink 6 Ink 7 Ink 8 Dye 11 Dye 2 1 Dye 3 1 Dye 4 1.5 Dye 5 1.5 Dye 6 1 Dye 7 1.5 Dye 8 1.5 BenzylAlcohol 10 10 10 10 10 10 12 10 2-Pyrollidone 20 20 20 20 20 20 20 20Resin 1 Resin 2 50 Resin 3 45 45 45 45 45 20 45 Water 24 24 19 23.5 23.524 43.5 23.5 Surfactant 3.0 Footnote: The resins were used as a 20% w/vsolution in water at pH 7.1.

The inks described above were printed onto different paper using aOlivetti JP 450 ink jet printer and tested as follows (the results aregiven in Table 2):

The Chroma and the OD of a print was measured using an X-Rite 938Spectrodensitometer;

the Lf (ΔE) was determined by the change in I.a.b coordinates asmeasured by an X-Rite 938 Spectrodensitometer after the print has beenirradiated for 100 hrs (ΔE) in a Atlas Ci35A Weatherometer, where a lowfigure indicates high light-fastness;

the WF was determined by running water (2 ml) down lines of print at anangle of approximately 45° immediately after the lines had been printedand the prints were given a score of 1-10 where 1 indicates poor wetfastness and 10 indicates no detected ink run down.

TABLE 2 Ink Paper Chroma OD LF WF 1 WC 58.17 0.86 30.3 10 1 XA 57.130.83 27.5 10 2 XA 62.35 1.117 22.43 10 2 WC 61.93 0.915 22.75 10 3 WC59.63 0.98 25.15 10 3 XA 58.29 0.952 24.21 10 4 XA 56.97 1.014 11.43 9.54 WC 61.21 1.101 11.71 9.5 5 XA 56.07 0.995 27.31 10 5 WC 58.71 1.02625.93 10 6 WC 64.31 1.14 26.29 10 6 XA 59.77 1.044 26.69 10 7 XA 54.011.013 29.97 8 7 HG201 63.31 1.224 18.93 9 8 WC 60.35 0.986 36.97 9.5 8XA 60.33 1.066 24.55 9.5

Further inks comprising the exemplified dyes and resins may be may beprepared having the formulations described in the following tables. Inthe tables the number in the first column (headed Ex. no.) denotes theexample number(s) of dye(s) to be used in the ink and the number in thesecond column indicates the parts per weight of the total dye added. Inthe third column “Resin#” identifies which of Resins 1, 2 and 3 was used(each resin comprising 20% solids and 80% water) with the number ofparts by weight of the resin being shown in brackets. Numbers quoted inthe third column onwards refer to the number of parts of the relevantingredient and all parts are by weight.

The following other abbreviations are used in the tables:

BZ=benzyl alcohol; DEG=diethylene glycol; NMP=N-methyl pyrollidone;TEN=triethanolamine; CAP=caprolactam; BUT=butylcellosolve; ACE=acetone;IPA=isopropanol; MEOH=methanol; 2P=pyrolidinone; MIBK=methylisobutylketone; TDG=thiodiglycol; PHO=K₂PO₄; FRU: fructose; SUR=Surfynol 465 (asurfactant); and DMB=diethylene glycol monobutyl ether.

TABLE 3 Ex. Resin No. Dye (parts) Water BZ DEG ACE 2P MIBK BUT 1 2.01(10) 58 6 4 10 10  1 2.1 2(6)  60.9  8 20 1 2 2 1.8 2(10) 63.2  5 15 52 5.0 3(4)  50.0 20 2 1 15 3 1 1.0 3(7)  63  5 4 15 5

TABLE 4 Ex. Resin no. Dye (parts) Water BZ DEG ACE NaOH IPA 2P 2 3.01(10) 62.8  5 4 0.2 25 1 5.0 2(15) 50 20 10 2 2.0 3(5)  60.7 10 10 0.3 3 10

TABLE 5 Ex. Resin (NH₄)₂ No. Dye (parts) Water BZ DEG ACE NaOH SO₄ 2PMIBK BUT 1 1.1 2(12) 61.9 9 0.5 0.5  9 5 1 2 4.1 3(10) 48.6 11 2 4 0.320

TABLE 6 Ex. Resin No. Dye (parts) Water BZ DEG ACE IPA MeOH 2P MIBK BUT1 + 2 5.0 3(5)  54 15  3 3 6 5 4 2 2.4 1(5)  51.6 5 4 6 20 5 1 1 3.22(4)  57.8 8 4 3 5 4 6 5 1 2.0 3(10) 73 6 2 2 1 4 2 3.3 2(12) 63.7 10  26 3

TABLE 7 Ex. Resin No. Dye (parts) Water BZ NMP FRU DMB CH₃NH₂ CAP 2 4.02(10) 67 10 14  1 4 0.2 1 2.2 2(10) 67 10 3 2 6 1 5.0 3(12) 54.4  5 17 7 2 4.0 3(20) 56  5 8 5 2 1 1.5 2(13) 71.5 2 12 

TABLE 8 Ex. Resin No. Dye (parts) Water BZ NMP TDG FRU PHO DMB CAP 1 2.52(15) 60  6 15 0.12 4 2 0.9 1(5)  63 10 20 0.5 0.2 1 2 2(10) 60 11 10 61 2 2.0 2(10) 56 10  5 12 5

TABLE 9 Ex. Resin No. Dye (parts) Water BZ NMP SUR TEN TDG FRU PHO DMB 11.5 1(10) 63 5 0.15 0.5 20 2 2.1 1(15) 65 5 5 0.1 0.2  2 0.5 0.1 5

TABLE 10 Ex. Resin No. Dye (parts) Water BZ NMP SUR TDG CH₃NH₂ CAP 1 3.13(10) 60 12 0.3 15 0.2 2 5.0 1(15) 43 15 15  5 2

TABLE 11 Ex. Resin No. Dye (parts) Water BZ NMP TEN TDG PHO DMB CH₃NH₂CAP 2 4.0 3(15) 59  9  7 0.5 0.95 5 1 5.0 1(5)  51 15 20 1 1 1 1

EXAMPLE 10 Dye 10

(a) Preparation of Coupling Component:

(i) 3-Aminoacetanilide (75.0 g) and crotonic acid (60.0 g) were mixedtogether and stirred for 16 hours at 80° C. The reaction mixture wascooled to 40° C. and ethyl acetate (400 ml) was added. The product wasextracted into 2 M sodium carbonate(1 liter) which was then adjusted topH 5 with conc. hydrochloric acid. The product was extracted into ethylacetate, dried (MgSO₄), filtered and evaporated to dryness to give abrown oil which was used directly in the next step.

(ii) The product from step (a)(i) above (35.4 g), iodoethane (26.5 g),calcium carbonate (1 7.0 g) and water were placed in a flask and heatedwith stirring at 70-80° C. for 22 hours. The hot reaction was filteredthrough kieselguhr and the cooled solution extracted withdichloromethane and evaporated to dryness to give a brown oil which wasused directly in the next step.

(iii) The product from step (a)(ii) above(10.0 g), chloroacetonitrile(5.68 g), potassium carbonate (5.24 g) and dimethyl formamide (100 ml)were mixed and heated at 80° C. for 45 hours. The reaction mixture waspoured onto water and extracted with ether to give the title couplingcomponent (13.84 g).

(b) Preparation of Dye 10

The method of Example 1, stage (b), was repeated except that in place of3-(N-n-butyl-N-sec-butylamino)acetanilide there was used the productfrom Example 10, Stage (a).

The crude product was isolated by extracting into dichloromethane andpurified by column chromatography on silica gel (a mixture of 15:85volume ratio methanol to dichloromethane, respectively, was used as theeluent) to give the title dye (6.09 g) as an oil having a λmax at 524nm.

EXAMPLE 11 Dye 11

Example 10 may be repeated except that in place of 3-aminoacetanilidethere is used 3-propionamido aniline.

EXAMPLE 12 Dye 12

(a) Preparation of Coupling Component.

(i) Zinc dust (30 g) was activated by stirring in 5% hydrochloric acid.The acid was removed and the zinc then washed with water, methanol andthen ether. The zinc dust was then slowly added to the flask containingacetic acid (85 ml), m-aminoacetamide (15 g) and ethyl acetoacetate (13ml). The reaction was stirred at 65° C. for 2 hours and then allowed tocool to room temperature. Methanol (50 ml) was added and the reactionmixture was filtered. The residue was washed with methanol and thecombined filtrates were evaporated to dryness. Ice/water (100 ml) anddichloromethane (100 ml) were added to the residue, the pH of themixture was adjusted to 10 with ammonia solution, and then the productwas isolated from the dichloromethane layer to give an oil (21.1 g).

(ii) The product from stage (i) above (9.39 g), iodoethane (5.2 ml),calcium carbonate (3.6 g) and water (100 ml) were placed in a flask andheated at 70° C. for 16 hours. The cooled reaction mixture was extractedwith dichloromethane to give the coupling component as a brown oil (10.3g)

(b) Preparation of Dye 12

The method of Example 1, stage (b), was repeated except that in place ofthe amine from Maybridge Chemical Company there was used from Example12, stage (a), and in place of 3-(N-n-butyl-N-sec-butylamino)acetanilide there was used the product of Example 2, stage (a).

EXAMPLE 13 Dye 13

(a) Preparation of 3-[N-(2-hydroxyethyl)-N-sec-butylamino]acetanilide.

(i) 3-(N-sec-Butylamino)acetanilide

3-aminoacetanilide (186.2 g), 2-bromobutane (198 g), triethylamine (150g) and ethanol (1 liter) were heated under reflux for 64 hours. Aftercooling to room temperature triethylamine hydrochloride was removed byfiltration and the solvent was evaporated under reduced pressure toleave a dark oil which was purified by chromatography on silica gel. Theproduct was crystallised by trituration under hexane to give 152 g ofproduct.

(ii) 3-[N-(2-hydroxyethyl)-N-sec-butylamino]acetanilide.

The product from stage (i) above (30 g), calcium carbonate (43.7 g),potassium iodide (7.3 g) and 2-chloroethanol (29.3 ml) in water (75 ml)were heated under reflux for 80 hours. The reaction mixture was allowedto cool, filtered and the residue washed with dichloromethane (2×100ml). The filtrates were extracted with dichloromethane and evaporated todryness to give a brown oil (29.0 g).

(b) Preparation of Dye 13

The method of Example 1, stage (b) was repeated except that in place ofthe amine from Maybridge Chemical Company there was used2-amino-5-cyanomethylthio-1,3,4-thiodiazole and in place of3-(N-n-butyl-N-sec-butylamino) acetanilide there was used the product ofExample 13, stage (a). Dye 13 was obtained as a dark green solid havinga λmax at 524 nm.

EXAMPLE 14 Dye 14

Dye 14 was prepared by the reaction of Dye 13 (1.09 g) with acetylchloride (0.54 ml) and piperidine (1 drop) in anhydrous dichloromethane(50 ml) for 4 hours at room temperature. The reaction mixture was washedwith water, 2 M sodium bicarbonate (300 ml) and water (300 ml) andevaporated to dryness to give the title dye (0.55 g) as a green solidhaving a λmax at 524 nm.

EXAMPLE 15 Preparation of Inks

The inks described in Table 12 were prepared by the general methoddescribed above in Example 9. All abbreviations used have the samemeanings as those in Example 9.

TABLE 12 Component Ink 3 Ink 4 Ink 5 Ink 6 Ink 7 Ink 8 Dye 10 1.5 1.51.5 1.5 Dye 12 0.3 1.5 Dye 13 1.2 1.5 Dye 14 1.5 1.5 Benzyl Alcohol 1014 12 10 10 11 2-Pyrollidone 20 18 20 20 20 19 Resin 1 45 Resin 2 45Resin 3 45 20 45 45 Water 23.5 21.5 43.5 23.5 23.5 23.5 Surfactant 3Footnote: The Resins were used as a 20% w/v solution in water at pH 7.1.

Certain of the inks described in Table 12 were printed onto paper andthe OD, LF and WF measured using the method described in Example 9. Theresults are shown in Table 13 below.

TABLE 13 Ink Paper Chroma OD LF WF 3 WC 57.0 0.88 22.2 9 3 XA 54.7 0.8619.6 9.5 5 XA 53.17 0.84 29.21 10 5 HG 201 67.81 1.19 38.55 10 6 WC57.05 0.99 32.57 9 6 XA 55.51 1.00 31.87 9 7 XA 57.25 0.98 14.19 9.5 7WC 60.53 1.03 15.75 9.5

Further inks comprising the exemplified dyes and resins may be may beprepared having the formulations described in the following tables. Inthe tables the number in the first column (headed Ex. no.) denotes theexample number(s) of dye(s) to be used in the ink and the number in thesecond column indicates the parts per weight of the total dye added. Inthe third column “Resin#” identifies which of Resins 1, 2 and 3 was used(each resin comprising 20% solids and 80% water) with the number ofparts by weight of the resin being shown in brackets. Numbers quoted inthe third column onwards refer to the number of parts of the relevantingredient and all parts are by weight.

The abbreviations used in the tables are as defined in Example 9 above:

TABLE 14 Ex. Resin No. Dye (parts) Water BZ DEG ACE 2P MIBK BUT 10 2.01(10) 58 6 4 10 10  10 2.1 2(6)  60.9  8 20 1 2 11 1.8 2(10) 63.2  5 155 11 5.0 3(4)  50.0 20 2 1 15 3 10 1.0 3(7)  63  5 4 15 5

TABLE 15 Ex. Resin no. Dye (parts) Water BZ DEG ACE NaOH IPA 2P 11 3.01(10) 52.8 15 4 0.2 15 10 5.0 2(15) 50 20 10 11 2.0 3(5)  65.7 10 5 0.3 3 10

TABLE 16 Ex. Resin (NH₄)₂ No. Dye (parts) Water BZ DEG ACE NaOH SO₄ 2PMIBK BUT 10 1.1 2(12) 61.9 9 0.5 0.5  9 5 1 11 4.1 3(10) 48.6 11 2 4 0.320

TABLE 17 Ex. Resin No. Dye (parts) Water BZ DEG ACE IPA MeOH 2P MIBK BUT10 + 11 5.0 3(5)  54 15 3 3 6  5 4 12 2.4 1(5)  51.6  5 4 6 20 5 1 133.2 2(4)  57.8  8 4 3 5 4  6 5 14 5.0 3(10) 60  6 2 2 1  4 10  12 1.32(12) 65.7 10  2 6 3

TABLE 18 Ex. Resin No Dye (parts) Water BZ NMP FRU DMB CH₃NH₂ CAP 12 4.02(10) 57 10 14  1 4 0.2 10 2.2 2(10) 67 10 3 2 6 10 5.0 3(12) 44.4 1517  7 11 4.0 3(20) 56  5 8 5 2 14 3.0 2(13) 65  5 2 12 

TABLE 19 Ex. Resin No. Dye (parts) Water BZ NMP TDG FRU PHO DMB CAP 102.5 2(15) 60  6 15 0.12 4 11 0.9 1(5)  63 10 20 0.5 0.2 13 5.0 2(10) 5711 10 6 1 13 2.0 2(10) 56 10  5 12 5

TABLE 20 Ex. Resin No. Dye (parts) Water BZ NMP SUR TEN TDG FRU PHO DMB10 1.5 1(10) 63  5 0.15 0.5 20 12 2.1 1(15) 55 15 5 0.1 0.2  2 0.5 0.1 5

TABLE 21 Ex. Resin No. Dye (parts) Water BZ NMP SUR TDG CH₃NH₂ CAP 103.1 3(10) 64  8 0.3 15 0.2 11 5.0 1(15) 43 15 15  5 2

TABLE 22 Ex. Resin No. Dye (parts) Water BZ NMP TEN TDG PHO DMB CH₃NH₂CAP 13 4.0 3(15) 59  9  7 0.5 0.95 5 13 5.0 1(5)  51 15 20 1 1 1 1

What is claimed is:
 1. A composition which comprises: (a) from 0.5 to 15parts in total of a dye of Formula (1):

R¹ and D are each independently H or a substituent; R² and R³ are eachindependently optionally substituted alky, aryl or aralkyl, or R² and R³together with the carbon atom to which they are attached form anoptionally substituted ring; R⁴ and R⁵ are each independently H oroptionally substituted alkyl, aryl or aralkyl; and R⁶ is optionallysubstituted alkyl, aryl or aralkyl: (b) from 0.2 to 25 parts of awater-dissipatable polymer; (c) from 40 to 90 parts of water, and (d)from 0 to 60 parts of organic solvent; wherein all parts are by weightand the total number of parts (a)+(b)+(c)+(d) add up to
 100. 2. Acomposition according to claim 1 wherein R² and R³ are free from thefollowing substituents: —NO₂, —CN, —Cl, —Br, —F, —OH, —OC₁₋₄-alkyl,—COOC₁₋₄—(CH₂)₁₋₄—CN, —CONH₂, —CONH(C₁₋₄-alkyl), —OCO(C₁₋₄-alkyl) and—COO(C₁₋₄-alkyl).
 3. A composition according to claim 1 wherein at leastone of R² and R³ carries a substituent and at least one of saidsubstituents is selected from the group consisting of: —NO₂, —CN, —Cl,—Br, —F, —OH, —OC₁₋₄-alkyl, —COOC₁₋₄—(CH₂)₁₋₄—CN, —CONH₂,—CONH(C₁₋₄-alkyl), —OCO(C₁₋₄-alkyl) and —COO(C₁₋₄-alkyl).
 4. Acomposition according to claim 1 wherein R¹ and D are each independentlyhalo; optionally substituted alkyl, aryl, aralkyl; or a group of formula—X—R⁷ wherein X is O, S, SO, SO₂, or NR⁸ wherein R⁷ and R⁸ are eachindependently H or optionally substituted alkyl, aryl or aralkyl.
 5. Acomposition according to claim 1 wherein R¹ and D are each independentlyhalo; optionally substituted C₁₋₆-alkyl; or a group of formula —X—R⁷wherein X is O, S, SO, SO₂, or NR⁸ wherein R⁸ is H or C₁₋₆-alkyl and R⁷is optionally substituted C₁₋₆-alkyl.
 6. A composition according toclaim 1 wherein R² and R³ are each independently optionally substitutedC₂-alkyl, or R² and R³ together with the carbon atom to which they areattached form an optionally substituted 5- or 6-membered ring.
 7. Acomposition according to claim 1 wherein R⁴ and R⁵ are eachindependently H or optionally substituted C₁₋₆-alkyl.
 8. A compositionaccording to claim 1 wherein said optional substituents are eachindependently selected from carboxy, sulpho, nitro, halo, alkyl, alkoxy,hydroxy, amine, mercapto, thioalkyl, cyano, ester and amide, with theproviso that R² and R³ are free from the following substituents: —NO₂,—CN, —Cl, —Br, —F, —OH, —OC₁₋₄-alkyl, —OC₁₋₄-alkylene—CN, —CONH₂,—CONH(C₁₋₄-alkyl), —COOC₁₋₄—(CH₂)₁₋₄—CN, —OCO(C₁₋₄-alkyl) and—COO(C₁₋₄-alkyl).
 9. A composition according to claim 1 wherein theorganic solvent comprises a mixture of a water-miscible organic solventand a water-immiscible organic solvent.
 10. A composition according toclaim 1 wherein the polymer is a water-dissipatable polyester.
 11. Acomposition according to claim 1 comprising two or more dyes at leastone of which is a dye of Formula (1).
 12. An ink jet printing inkaccording to any one of the preceding claims.
 13. A process for printingan image on a substrate comprising applying thereto, by means of an inkjet printer, a composition according to claim
 1. 14. A paper, anoverhead projector slide or a textile material printed with acomposition according to claim
 1. 15. A cartridge suitable for use in anink jet printer containing a composition according to claim
 1. 16. Anink jet printer containing a composition according to claim 1.